Semiconductor photoresist composition and method of forming pattern using the same

Abstract

A semiconductor photoresist composition includes: an organotin compound represented by Chemical Formula 1; and a solvent, wherein the detailed description of Chemical Formula 1 is as described in the specification. In addition, a method of forming a pattern includes: forming an etching target layer on a substrate; coating the semiconductor photoresist composition on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask. Chemical formula 1 # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0103690 filed in the Korean Intellectual Property Office on August 8, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] One or more aspects of the embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming (or providing) a pattern using the semiconductor photoresist composition. Background Art

[0004] Extreme ultraviolet (EUV) lithography is considered an important (even necessary) technology for manufacturing next-generation semiconductor devices. EUV lithography is a pattern forming (or providing) technology that uses EUV rays with a wavelength of about 13.5 nm as an exposure source. When EUV lithography is applied, very fine patterns (e.g., less than or equal to about 20 nm) can be formed in the exposure process during the manufacture of semiconductor devices.

[0005] Extreme ultraviolet (EUV) lithography is accomplished (e.g., performed by developing a compatible photoresist) wherein the development (e.g., the process of developing the photoresist) can be performed with a spatial resolution of less than or equal to about 16 nm. Currently, efforts are being made to overcome or mitigate the inadequate or unsuitable specifications of chemically amplified (CA) photoresists for next generation devices, such as resolution, photospeed, and / or feature roughness (also referred to as line edge roughness or LER).

[0006] Intrinsic image blurring due to acid-catalyzed reactions in polymer-type or class photoresists may limit resolution of small feature sizes, a phenomenon well known to occur in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed to achieve relatively high sensitivity, but may have more difficulties under EUV exposure in part because their typical elemental composition can reduce the absorbance of the photoresist at a wavelength of about 13.5 nm and thus reduce its sensitivity.

[0007] In one or more embodiments, CA photoresists may have difficulty with small feature sizes due to roughness issues, and experiments often show that the line edge roughness (LER) of CA photoresists increases as photospeed decreases due, at least in part, to the nature (e.g., properties) of the acid catalyst process. Therefore, due to these deficiencies and problems with CA photoresists, a new relatively high performance photoresist is desired or needed in the semiconductor industry.

[0008] In order to overcome the above-mentioned disadvantages of chemically amplified (CA) organic photosensitive compositions, an inorganic photosensitive composition has been developed. The inorganic photosensitive composition is mainly used for negative patterning, which resists removal by a developer composition due to chemical modification by a non-chemical amplification mechanism. The inorganic composition contains an inorganic element having a higher EUV absorption rate than hydrocarbons, and thus can ensure sensitivity (e.g., sensitivity to EUV light) by a non-chemical amplification mechanism, and furthermore can be less sensitive to stochastic effects, and thus can have relatively low line edge roughness and a relatively small number of defects.

[0009] Inorganic photoresists based on peroxypolyacids of tungsten mixed with tungsten, niobium, titanium and / or tantalum have been reported as radiation-sensitive materials for patterning (see also US 5061599 as an example; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986; the entire contents of each of the two examples are incorporated herein by reference).

[0010] These materials can be used or adapted to pattern large pitches of bilayer configurations as effectively as extreme ultraviolet (deep UV), X-ray and / or electron beam sources. Recently, improved performance has been obtained if cationic hafnium metal oxide sulfate (HfSOx) materials are used with peroxy complexing agents for imaging 15 nm half-pitch (HP) by projection EUV exposure (e.g., when cationic hafnium metal oxide sulfate (HfSOx) materials are used with peroxy complexing agents for imaging 15 nm half-pitch (HP) by projection EUV exposure) (see also US2011-0045406 as examples; J.K. Stowers, A. T. Lecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau (JK Stowers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, Proc. SPIE, 7969, 796915, 2011; the entire contents of each of the two examples are incorporated herein by reference). This system exhibits relatively high performance for non-CA photoresists and has a feasible photosensitivity close to that required (or needed) for EUV photoresists. However, hafnium metal oxide sulfate materials with peroxy complexing agents have some practical disadvantages. First, these materials are coated in the form of a mixture of corrosive sulfuric acid / hydrogen peroxide and have insufficient or unsuitable shelf life stability. Second, as a composite mixture, structural changes to achieve performance improvements are not easily achieved. Third, development should be performed in a relatively very high concentration of about 25 wt % tetramethylammonium hydroxide (TMAH) solution and / or similar solutions.

[0011] Recently, research has been conducted to explore tin-containing molecules because they can have excellent or suitable absorption of extreme ultraviolet rays. Among organotin polymer compounds, alkyl ligands can be dissociated by light absorption and / or secondary electrons generated thereby, and can be cross-linked with adjacent chains through oxygen bonds, thereby enabling negative patterning that can not be removed by organic developers. Such organotin polymers can show greatly improved sensitivity while maintaining suitable resolution and line edge roughness, but their patterning characteristics need to be further improved for commercial viability. Summary of the invention

[0012] One or more aspects of embodiments of the present disclosure are directed to a semiconductor photoresist composition having excellent or appropriate sensitivity, improved moisture-proof storage stability, and improved coating characteristics.

[0013] One or more aspects of the embodiments of the present disclosure relate to a method of forming (or providing) a pattern using the semiconductor photoresist composition.

[0014] Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from reading the description, or may be learned by practice of the presented embodiments of the disclosure.

[0015] The semiconductor photoresist composition according to one or more embodiments includes an organic tin compound represented by Chemical Formula 1 and a solvent.

[0016] Chemical formula 1

[0017]

[0018] In Chemical Formula 1,

[0019] R 1 It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or L a -OR a (where L a may be a substituted or unsubstituted C1 to C20 alkylene group, and R a may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group),

[0020] R 2 It may be halogen, alkoxy and / or aryloxy (e.g., -OR b , where R b The alkyl group may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (e.g., any suitable) combination thereof), a carboxyl group (e.g., —O(CO)R 6 , where R 6The amino group may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof), alkylamino, and / or dialkylamino (e.g., —NR 7 R 8 , where R 7 and R 8 The alkyl groups may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof), an amide group (e.g., -NR 9 (COR 10 ), where R 9 and R 10 The alkyl radicals may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof), an amidino group (e.g., —NR 11 C(NR 12 )R 13 , where R 11 , R 12 and R 13 may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof),

[0021] R 3 to R 5 and L may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or L c -OR c (where L c may be a substituted or unsubstituted C1 to C20 alkylene group, and R c may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), and

[0022] n is an integer from 1 to 3.

[0023] According to one or more embodiments, the method of forming (or providing) a pattern includes: forming (or providing) an etching target layer on a substrate; coating the semiconductor photoresist composition on the etching target layer to form (or provide) a photoresist layer; patterning the photoresist layer to form (or provide) a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask.

[0024] The semiconductor photoresist composition according to one or more embodiments may provide a photoresist pattern having improved moisture-proof storage stability and improved coating characteristics and sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] These and / or other aspects will become apparent and more easily understood by reading the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0026] Figures 1 to 5 Each is a cross-sectional view for explaining a method of forming (or providing) a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0027] [Explanation of Reference Numerals]

[0028] 100: Substrate

[0029] 102: Film

[0030] 104: Resist base

[0031] 106: Photoresist layer

[0032] 106a: Unexposed area

[0033] 106b: Exposure area

[0034] 108: Photoresist pattern

[0035] 110: Patterned mask

[0036] 112: Organic layer pattern

[0037] 114: Thin film pattern DETAILED DESCRIPTION

[0038] In the following, embodiments of the present disclosure are described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, for the sake of clarity of the present disclosure, functions or structures well known to those skilled in the art will not be described in detail.

[0039] In order to clearly illustrate the present disclosure, some descriptions and relationships are not provided, and the same or similar configuration elements are represented by the same reference numerals throughout the disclosure. In addition, since the size and thickness of each configuration shown in the drawings are arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0040] In the drawings, the thickness of each layer, film, panel, region, etc. may be exaggerated for clarity. In the drawings, the thickness of a portion of each layer, region, etc. may be exaggerated for clarity. It should be understood that if an element (such as a layer, film, region, or substrate) is referred to as being "on" another element (for example, when an element (such as a layer, film, region, or substrate) is referred to as being "on" another element), the element may be directly on the other element (for example, without any intermediate elements therebetween), or intermediate elements may also be present.

[0041] It should be understood that although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish between various elements. Therefore, without departing from the teachings of the present invention, the first element may be referred to as the second element. Similarly, the second element may be referred to as the first element.

[0042] As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0043] It will also be understood that the terms “includes / including” and / or “comprises / comprising”, when used in the present specification, specify the presence of stated features, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components and / or groups thereof.

[0044] As used herein, the terms "use," "using," and "used" may be considered synonymous with the terms "utilize," "utilizing," and "utilized," respectively.

[0045] As used herein, expressions such as "at least one of," "one of," and "selected from," when preceding a series of elements, modify the entire series of elements rather than the individual elements in the series. For example, "at least one selected from a, b, and c," "at least one of a, b, or c," and "at least one of a, b, and / or c" may indicate including only a, only b, only c, including (e.g., simultaneously) both a and b, including (e.g., simultaneously) both a and c, including (e.g., simultaneously) both b and c, including all of a, b, and c, or variations thereof.

[0046] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0047] In addition, the use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure.”

[0048] For ease of description, spatially relative terms such as "beneath," "below," "lower," "above," "upper," "bottom," "top," and the like may be used herein to describe the relationship of one element or feature shown in the figures to another (other) element or feature. It should be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation shown in the figures. For example, if the device in the figure is turned over, the elements described as being "below" or "beneath" other elements or features will now be oriented "above" or "on" the other elements or features. Thus, the term "below" may include both above and below orientations. The device may be oriented in other ways (rotated 90 degrees or other orientations), and the spatially relative descriptors used herein should be interpreted accordingly.

[0049] As used herein, the terms "substantially," "about," and similar terms are used as terms of approximation rather than degree, and are intended to account for the inherent deviations in measured or calculated values ​​that one of ordinary skill in the art would recognize. "About" or "approximately" as used herein include the stated value and mean within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

[0050] Any numerical range described herein is intended to include all sub-ranges of the same numerical precision that fall within the range. For example, the range of "1.0 to 10.0" is intended to include all sub-ranges between (and including) the minimum value 1.0 and the maximum value 10.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as (for example) 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits that fall within it, and any minimum numerical limit described in this specification is intended to include all higher numerical limits that fall within it. Therefore, the applicant reserves the right to amend this specification (including the claims) to explicitly state any sub-ranges that fall within the range explicitly stated herein.

[0051] The term "substituted" as used herein refers to a hydrogen atom replaced by deuterium, halogen, hydroxyl, thiol, cyano, nitro, -NRR' (wherein R and R' can each independently be hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" can each be independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group). Each is independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilanyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 thioether group, and / or (for example, any suitable) combination thereof. “Unsubstituted” means that a hydrogen atom is not replaced by another substituent and remains as a hydrogen atom.

[0052] If no definition is provided otherwise (eg, when no definition is provided otherwise), the "alkyl" described herein refers to a straight chain or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" without any double bond or triple bond.

[0053] The alkyl group may be a C1 to C10 alkyl group. For example, the alkyl group may be a C1 to C8 alkyl group, a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and / or a 2,2-dimethylpropyl group.

[0054] If a definition is not otherwise provided (eg, when a definition is not otherwise provided), "cycloalkyl" as described herein refers to a monovalent cyclic aliphatic hydrocarbon group.

[0055] The cycloalkyl group may be a C3 to C10 cycloalkyl group, such as a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and / or a cyclohexyl group, but the present disclosure is not limited thereto.

[0056] The "aryl group" described herein refers to a substituent in which all atoms in a cyclic substituent have p orbitals and these p orbitals are conjugated, and may include a monocyclic or condensed-ring polycyclic (ie, rings sharing adjacent pairs of carbon atoms) functional groups.

[0057] Unless otherwise defined, the "alkenyl group" described herein refers to an aliphatic unsaturated alkenyl group including at least one double bond in a straight or branched aliphatic hydrocarbon group.

[0058] Unless otherwise defined, "alkynyl" described herein refers to an aliphatic unsaturated alkynyl group including at least one triple bond in a straight or branched aliphatic hydrocarbon group.

[0059] In the chemical formulas set forth herein, t-Bu refers to tert-butyl.

[0060] Hereinafter, semiconductor photoresist compositions according to one or more embodiments are described.

[0061] The semiconductor photoresist composition according to one or more embodiments includes an organic tin compound represented by Chemical Formula 1 and a solvent.

[0062] Chemical formula 1

[0063]

[0064] In Chemical Formula 1,

[0065] R 1It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or L a -OR a (Where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group),

[0066] R 2 It may be halogen, alkoxy and / or aryloxy (e.g., -OR b , where R b The alkyl group may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (e.g., any suitable) combination thereof), a carboxyl group (e.g., —O(CO)R 6 , where R 6 The amino group may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof), alkylamino, and / or dialkylamino (e.g., —NR 7 R 8 , where R 7 and R 8 The alkyl groups may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof), an amide group (e.g., -NR 9 (COR 10 ), where R 9 and R 10 The alkyl radicals may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof), an amidino group (e.g., —NR 11 C(NR 12 )R13 , where R 11 , R 12 and R 13 may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable) combination thereof),

[0067] R 3 to R 5 and L may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or L c -OR c (Where L c may be a substituted or unsubstituted C1 to C20 alkylene group, and R c may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), and

[0068] n is an integer from 1 to 3.

[0069] The compound of the present disclosure includes a bidentate bond formed by an acetylacetone ligand and a central metal tin, so that two oxygen atoms are stably or appropriately coordinated to the central metal, thereby improving sensitivity and moisture-proof storage stability.

[0070] For example, n may be an integer of 1 or 2.

[0071] The organotin compound according to the present disclosure may also include an ultraviolet group and a photosensitive reactive group jointly (eg, simultaneously) in addition to the acetylacetone ligand linked to tin as a central metal.

[0072] For example, R 1 It may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or L a -OR a (Where L a may be a substituted or unsubstituted C1 to C10 alkylene group, and R a may be a substituted or unsubstituted C1 to C10 alkyl group).

[0073] For example, R1 It may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted vinyl group, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, and / or (e.g., any suitable) combination thereof, and

[0074] R a The group may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, and / or (e.g., any suitable) combination thereof.

[0075] For example, R 2 It may be halogen, alkyloxy and / or aryloxy (e.g., -OR b , where R b The alkyl group may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, and / or (e.g., any suitable) combination thereof), a carboxyl group (e.g., —O(CO)R 6 , where R 6 The amino group may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof), alkylamino, and / or dialkylamino (e.g., —NR 7 R 8 , where R 7 and R 8The alkyl groups may each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof), an amide group (e.g., -NR 9 (COR 10 ), where R 9 and R 10 The alkyl radicals may each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof), an amidino group (e.g., -NR 11 C(NR 12 )R 13 , where R 11 , R 12 and R 13 Each may independently be hydrogen, substituted or unsubstituted C1 to 10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof).

[0076] For example, R 2 It can be halogen, alkyloxy and / or aryloxy (e.g. -OR b , where R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, and / or (e.g., any suitable) combination thereof), a carboxyl group (e.g., —O(CO)R 6 , where R 6 It may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof).

[0077] In one or more embodiments, R 2 It can be a carboxyl group (-O(CO)R 6 , where R 6It may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof).

[0078] For example, R b may be substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, and / or (e.g., any suitable) combination thereof, and

[0079] R 6 The radical may be hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, and / or any suitable combination thereof.

[0080] For example, R 3 to R 5The radicals may each independently be hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, and / or (e.g., any suitable) combination thereof.

[0081] The organic tin compound may be represented by any one selected from the compounds listed in Group 1.

[0082] Group 1

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] The organotin compound strongly or moderately absorbs extreme ultraviolet light at about 3.5 nm, and may have excellent or moderate sensitivity to high energy light.

[0089] In the semiconductor photoresist composition according to one or more embodiments, the organic tin compound may be present in an amount of about 1 wt % to about 30 wt %, such as about 1 wt % to about 25 wt %, such as about 1 wt % to about 20 wt %, such as about 1 wt % to about 15 wt %, such as about 1 wt % to about 10 wt %, or such as about 1 wt % to about 5 wt %, based on 100 wt % of the semiconductor photoresist composition, but the present disclosure is not limited thereto. If the content (e.g., amount) of the organic tin compound is within any of the above ranges (e.g., when the content (e.g., amount) of the organic tin compound is within any of the above ranges), the storage stability and etching resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.

[0090] Since the photoresist composition according to one or more embodiments of the present disclosure includes the organic tin compound according to the embodiments of the present disclosure, a semiconductor photoresist composition having excellent or appropriate sensitivity and stability may be provided.

[0091] The solvent of the semiconductor photoresist composition according to one or more embodiments may be an organic solvent and may be, for example, selected from the following: aromatic compounds (e.g., xylene, toluene and / or similar compounds), alcohols (e.g., 4-methyl-2-pentenol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol and / or similar alcohols), ethers (e.g., anisole, tetrahydrofuran and / or similar ethers), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate and / or similar esters), ketones (e.g., methyl ethyl ketone, 2-heptanone and / or similar ketones) and / or (e.g., any suitable) mixtures thereof, but the present disclosure is not limited thereto.

[0092] The semiconductor resist composition according to one or more embodiments may further include a resin in addition to the organometallic compound, the vinyl-containing acid compound, and the solvent.

[0093] The resin may be a phenolic resin including at least one aromatic moiety of Group 2 (eg, at least one selected from the aromatic moieties of Group 2).

[0094] Group 2

[0095]

[0096] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0097] The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on the total amount (100 wt %) of the semiconductor photoresist composition.

[0098] If the resin is included in the above content (eg, amount) range (eg, when the resin is included in the above content (eg, amount) range), the semiconductor photoresist composition may have excellent or appropriate etching resistance and heat resistance.

[0099] The semiconductor photoresist composition according to one or more embodiments may include the aforementioned organometallic compound, solvent and resin (e.g., composed of the aforementioned organometallic compound, solvent and resin). However, in some embodiments, the semiconductor photoresist composition according to the embodiments of the present invention may also include additives. Examples of additives may be surfactants, cross-linking agents, leveling agents, organic acids, quenchers and / or (e.g., any suitable) combinations thereof.

[0100] The surfactant may include, for example, alkylbenzene sulfonate, alkyl pyridinium salt, polyethylene glycol, quaternary ammonium salt, and / or (eg, any suitable) combination thereof, but the present disclosure is not limited thereto.

[0101] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic crosslinking agent, an epoxy resin-based crosslinking agent, and / or a polymer-based crosslinking agent, but the present disclosure is not limited thereto. The crosslinking agent may have at least two substituents that form crosslinks, such as compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, polyurethane acrylate, acryl methacrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or similar compounds.

[0102] The leveling agent may be used to improve coating flatness during printing, and may be any suitable leveling agent (eg, a commercially available leveling agent).

[0103] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, and / or (e.g., any suitable) combinations thereof, but the present disclosure is not limited thereto.

[0104] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, and / or (eg, any suitable) combinations thereof.

[0105] The amount of the corresponding additive can be controlled or selected depending on the desired or suitable properties.

[0106] In one or more embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (e.g., to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, for example: a silane compound including a carbon-carbon unsaturated bond (e.g., vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane and / or vinyl tri(β-methoxyethoxy)silane); 3-methacryloxypropyl trimethoxysilane; 3-acryloxypropyl trimethoxysilane; p-phenylyl trimethoxysilane; 3-methacryloxypropyl methyl dimethoxysilane; 3-methacryloxypropyl methyl diethoxysilane; trimethoxy [3- (phenylamino) propyl] silane and / or similar silane compounds, but the present disclosure is not limited thereto.

[0107] Semiconductor photoresist composition can be formed into a pattern with a relatively high aspect ratio without collapse. Therefore, in order to form (or provide) a fine pattern with a width of, for example, about 5 nanometers (nm) to about 100nm, for example, about 5nm to about 80nm, for example, about 5nm to about 70nm, for example, about 5nm to about 50nm, for example, about 5nm to about 40nm, for example, about 5nm to about 30nm or about 5nm to about 20nm, the semiconductor photoresist composition can be used for a photoresist process using a wavelength in the range of about 5nm to about 150nm, for example, about 5nm to about 100nm, about 5nm to about 80nm, about 5nm to about 50nm, about 5nm to about 30nm or about 5nm to about 20nm. Therefore, the semiconductor photoresist composition according to one or more embodiments can be used to realize extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5nm.

[0108] According to one or more embodiments, a method for forming (or providing) a pattern using a semiconductor photoresist composition according to an embodiment of the present invention is provided. For example, the pattern produced may be a photoresist pattern.

[0109] According to one or more embodiments, the method of forming (or providing) a pattern includes: forming (or providing) an etching target layer on a substrate; coating the semiconductor photoresist composition on the etching target layer to form (or provide) a photoresist layer; patterning the photoresist layer to form (or provide) a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask.

[0110] In the following, reference is made to Figures 1 to 5 A method for forming (or providing) a pattern using the semiconductor photoresist composition is described. Figures 1 to 5 is a cross-sectional view for explaining a method of forming (or providing) a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0111] Reference Figure 1 , preparing an object to be etched. The object to be etched may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object to be etched is limited to the thin film 102. The entire (e.g., the entire or substantially the entire) surface of the thin film 102 is cleaned to remove impurities and / or the like remaining on the surface. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0112] Subsequently, a resist base layer composition for forming (or providing) the resist base layer 104 is spin-coated on the surface of the cleaned thin film 102. However, one or more embodiments are not limited thereto, and one or more suitable coating methods, such as spray coating, dip coating, blade coating, printing methods (e.g., inkjet printing and / or screen printing), and / or the like, may be used.

[0113] Hereinafter, a process including coating of a resist bottom layer is described. However, in some embodiments, a coating process of a resist bottom layer may not be provided (eg, may be omitted).

[0114] Then, the applied composition is dried and baked to form (or provide) a resist bottom layer 104 on the thin film 102. The baking may be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0115] The resist bottom layer 104 is formed between the substrate 100 and the photoresist layer 106, and therefore, if radiation reflected from the interface between the substrate 100 and the photoresist layer 106 and / or the hard mask between the layers is scattered into an unintended (or unexpected) photoresist area (for example, when the radiation is scattered into an unintended (or unexpected) photoresist area), non-uniformity in pattern forming (or providing) capability and non-uniformity in photoresist line width can be prevented or reduced.

[0116] Reference Figure 2 , a photoresist layer 106 is formed by coating a semiconductor photoresist composition on the resist bottom layer 104. The photoresist layer 106 can be obtained by coating the semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it through heat treatment.

[0117] For example, forming a pattern using a semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 coated with the thin film 102. The semiconductor photoresist composition may be coated by spin coating, slit coating, inkjet printing and / or the like and then dried to form the photoresist layer 106.

[0118] The semiconductor photoresist composition has been described herein and will not be described again in detail.

[0119] Subsequently, a first baking process is performed on the substrate 100 having the photoresist layer 106. The first baking process may be performed at about 80°C to about 120°C.

[0120] Reference Figure 3 , the patterned mask 110 may be used to selectively expose the photoresist layer 106 .

[0121] For example, exposure can use activating radiation using the following light: light with a relatively high energy wavelength, such as extreme ultraviolet (EUV; wavelength of about 13.5nm), electron beam (E-Beam), etc.; and such as i-line (wavelength of about 365nm), KrF excimer laser (wavelength of about 248nm), ArF excimer laser (wavelength of about 193nm), etc.

[0122] For example, light used for exposure according to one or more embodiments may have a wavelength in the range of about 5 nm to about 150 nm and a relatively high energy wavelength, such as extreme ultraviolet (EUV; wavelength 13.5 nm), electron beam (E-Beam), etc.

[0123] The exposed region 106 b of the photoresist layer 106 has a different solubility from the unexposed region 106 a of the photoresist layer 106 , wherein the exposed region 106 b forms a polymer through a cross-linking reaction (eg, condensation between organic metal compounds).

[0124] Subsequently, a second baking process is performed on the substrate 100. The second baking process may be performed at a temperature of about 90° C. to about 200° C. Due to the second baking process, the exposed region 106 b of the photoresist layer 106 becomes substantially insoluble in a developer (eg, a developing composition).

[0125] exist Figure 4 In the process, the unexposed area 106a of the photoresist layer is dissolved and removed by a developer to form (or provide) a photoresist pattern 108. For example, an organic solvent such as 2-heptanone and / or the like is used to dissolve and remove the unexposed area 106a of the photoresist layer to complete the photoresist pattern 108 corresponding to the negative image.

[0126] As described above, the developer (e.g., developer composition) used in the method for forming (or providing) a pattern according to one or more embodiments may be an organic solvent. The organic solvent used in the method for forming (or providing) a pattern according to one or more embodiments may be, for example, selected from: ketones (e.g., methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or similar ketones), alcohols (e.g., 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and / or similar alcohols), esters (e.g., propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or similar esters), aromatic compounds (e.g., benzene, xylene, toluene, and / or similar aromatic compounds) and / or (e.g., any suitable) combinations thereof.

[0127] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative image, but may also be formed to have a positive image. Herein, the developer used to form (or provide) a positive image may be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and / or (e.g., any suitable) combination thereof.

[0128] As described above, exposure to light having relatively high energy such as extreme ultraviolet (EUV; wavelength of 13.5 nm), electron beam (E-Beam), and light having a certain wavelength such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), etc. can provide a photoresist pattern 108 having a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0129] In some embodiments, the photoresist pattern 108 may have a half pitch less than or equal to about 50 nm, for example, less than or equal to about 40 nm, for example, less than or equal to about 30 nm, for example, less than or equal to about 20 nm, for example, less than or equal to about 15 nm, and the photoresist pattern 108 may have a line width roughness less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm.

[0130] Subsequently, the resist bottom layer 104 is etched using the photoresist pattern 108 as an etching mask. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

[0131] Reference Figure 5The exposed thin film 102 is etched by using the photoresist pattern 108 as an etching mask. Thus, the thin film is formed into a thin film pattern 114.

[0132] The etching of the thin film 102 may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 and / or a mixed gas thereof.

[0133] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 may have a width corresponding to the width of the photoresist pattern 108, wherein the photoresist pattern 108 is formed by the exposure process performed using the EUV light source. For example, the thin film pattern 114 may have a width of 5 nm to 100 nm, which is equal to the width of the photoresist pattern 108. For example, like the width of the photoresist pattern 108 (which is formed by the exposure process performed using the EUV light source), the thin film pattern 114 formed using the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm, and more specifically may have a width less than or equal to about 20 nm.

[0134] Hereinafter, the present disclosure will be described in more detail by way of an example of the preparation of a semiconductor photoresist composition according to an embodiment of the present invention. However, the present disclosure is not technically limited by the following examples.

[0135] Synthesis of Organotin Compounds

[0136] Synthesis Example 1: Synthesis of the compound represented by Chemical Formula 2

[0137] 10 g of tin t-butyl trisisopropoxide was placed in a 100 mL Schlenk flask, and 31 mL of anhydrous dichloromethane was added, followed by stirring at 0° C. in a nitrogen atmosphere.

[0138] 6.3 g of acetylacetone was slowly added at 0° C. The solution was stirred at room temperature for 3 hours. The solution temperature was lowered to 0° C., 1.89 g of acetic acid was slowly added, and stirred at room temperature for 12 hours.

[0139] The reaction solution was added with n-hexane and stored at low temperature to produce a solid.

[0140] The solid was filtered and washed with n-hexane under a nitrogen atmosphere to obtain a compound represented by Chemical Formula 2 in the form of a white solid.

[0141] Chemical formula 2

[0142]

[0143] Synthesis Example 2: Synthesis of the compound represented by Chemical Formula 3

[0144] 10 g of tert-butyltin triisopropoxide was placed in a 100 mL Schlenk flask, and 31 mL of anhydrous dichloromethane was added, followed by stirring at 0° C. in a nitrogen atmosphere.

[0145] A solution of 3.15 g of acetylacetone and 3.78 g of acetic acid was slowly added at 0°C, and the mixture was stirred at room temperature for 12 hours.

[0146] The reaction solution was concentrated under reduced pressure to remove dichloromethane, thereby obtaining a compound represented by Chemical Formula 3.

[0147] Chemical formula 3

[0148]

[0149] Synthesis Example 3: Synthesis of the compound represented by Chemical Formula 4

[0150] 10 g of tert-butyltin triisopropoxide was placed in a 100 mL Schlenk flask, and 31 mL of anhydrous dichloromethane was added, followed by stirring at 0° C. in a nitrogen atmosphere.

[0151] 6.3 g of acetylacetone were slowly added at 0° C. The solution was stirred at room temperature for 3 hours.

[0152] The reaction solution was added with n-hexane and stored at low temperature to produce a solid.

[0153] The solid was filtered and washed with n-hexane under a nitrogen atmosphere to obtain a compound represented by Chemical Formula 4 in the form of a white solid.

[0154] Chemical formula 4

[0155]

[0156] Synthesis Example 4: Synthesis of the compound represented by Chemical Formula 5

[0157] 10 g of tert-butyltin triisopropoxide was placed in a 100 mL Schlenk flask, and 31 mL of anhydrous dichloromethane was added, followed by stirring at 0° C. in a nitrogen atmosphere.

[0158] 3.15 g of acetylacetone was slowly added at 0°C, and the mixture was stirred at room temperature for 3 hours.

[0159] The reaction solution was concentrated under reduced pressure to remove dichloromethane, thereby obtaining a compound represented by Chemical Formula 5.

[0160] Chemical formula 5

[0161]

[0162] Comparative Synthesis Example 1

[0163] 8.5 g of nBuSnCl3 (butyl tin trichloride) was dissolved in anhydrous pentane, and the temperature was lowered to 0° C. Thereafter, 10.0 g of trimethylamine was slowly added dropwise, and then 4.2 g of ethanol was added and stirred at room temperature for 5 hours. When the reaction was completed, it was filtered, concentrated and vacuum dried to obtain a compound represented by Chemical Formula 6.

[0164] Chemical formula 6

[0165]

[0166] Comparative Synthesis Example 2

[0167] The compound represented by Chemical Formula 7 was obtained by performing synthesis in substantially the same manner as in Comparative Synthesis Example 1, except that BnSnCl 3 (benzyltin trichloride) was used instead of nBuSnCl 3 used in Comparative Synthesis Example 1.

[0168] Chemical formula 7

[0169]

[0170] (Preparation of semiconductor photoresist composition)

[0171] Examples 1 to 4 and Comparative Examples 1 and 2

[0172] The compounds represented by Chemical Formula 2 to Chemical Formula 5 obtained in Synthesis Examples 1 to 4 and the compounds represented by Chemical Formula 6 and Chemical Formula 7 obtained in Comparative Synthesis Examples 1 and 2 were respectively dissolved in 4-methyl-2-pentanol and filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a photoresist composition.

[0173] A 4-inch diameter circular silicon wafer with a native oxide surface was used as a substrate for thin film deposition. Prior to depositing the resist film, the wafer was treated in a UV ozone cleaning system for 10 minutes, the resist composition was spin-coated on the wafer at 1500 rpm for 30 seconds, and baked at 120° C. for 120 seconds to form (or provide) a thin film. Then, the thickness of the film after coating and firing was measured by an ellipsometer, and it was found that the thickness of the film in Examples 1 to 4 was about 25 nm, while the thickness of the film in Comparative Examples 1 and 2 was about 20 nm.

[0174] Assessment 1: Sensitivity Assessment

[0175] The substrate deposited with the resist film was exposed to an electron beam with an accelerating voltage of 100Kv to form (or provide) nanowires with a half pitch of 40nm. The irradiated substrate was exposed to 40°C for 30 seconds, then immersed in a petri dish containing 2-heptanone for 60 seconds, the substrate was taken out, the substrate was cleaned with the same solvent for about 10 seconds, and finally baked at 150°C. In order to confirm the pattern performance of the patterned substrate, the critical dimension (CD) of the formed line was measured using a field emission scanning electron microscopy (FE-SEM) image. At 1000Uc / cm 2 Under energy, if the CD size is greater than or equal to 40nm, the sensitivity is expressed as ◎, if the CD size is greater than or equal to 35nm, the sensitivity is expressed as ○, and if the CD size is less than 35nm, the sensitivity is expressed as △.

[0176] Assessment 2: Storage stability assessment

[0177] The storage stability of the organometallic compounds used in Examples 1 to 4 and Comparative Examples 1 and 2 was evaluated based on the following judgment criteria, and the results are shown in Table 1.

[0178] Storage stability

[0179] When the semiconductor photoresist compositions according to Examples 1 to 4 and Comparative Examples 1 and 2 were left at room temperature (20±5° C.) for a period of time, the degree of precipitation was visually observed and evaluated according to the storage standard.

[0180] ※Evaluation criteria

[0181] -◎: can be stored for more than or equal to 4 months

[0182] -○: Can be stored for more than or equal to 3 months and less than 4 months

[0183] -△: can be stored for more than or equal to two weeks and less than three months

[0184] -X: can be stored for less than two weeks

[0185] (Table 1)

[0186] Organotin compounds Storage stability Sensitivity Example 1 Chemical formula 2 ◎ ◎ Example 2 Chemical formula 3 ○ ◎ Example 3 Chemical formula 4 ○ ○ Example 4 Chemical formula 5 △ ○ Comparative Example 1 Chemical formula 6 X ○ Comparative Example 2 Chemical formula 7 X △

[0187] As can be seen from the results in Table 1, the semiconductor photoresist composition according to the Examples has excellent or appropriate sensitivity and significantly improved storage stability compared to the Comparative Examples.

[0188] In the above, some embodiments of the present disclosure have been described and illustrated. However, it is obvious to those skilled in the art that the present disclosure is not limited to the one or more embodiments described, but various appropriate modifications and changes can be made without departing from the spirit and scope of the present disclosure. Therefore, the modified or changed embodiments themselves may not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalent forms.

Claims

1. A semiconductor photoresist composition comprising: an organotin compound represented by Chemical Formula 1; and Solvents, Chemical formula 1 In Chemical Formula 1, R 1 is a substituted or unsubstituted C1 to C20 alkyl group, Substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, L a -OR a , where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, R 2 for Halogen, or -OR b , where R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, -O(CO)R 6 , where R 6 is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, -NR 7 R 8 , where R 7 and R 8 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, -NR 9 (COR 10 ), where R 9 and R 10 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, or -NR 11 C(NR 12 )R 13 , where R 11 , R 12 and R 13 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, R 3 to R 5 are each independently hydrogen, Substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, L c -OR c , where L c is a substituted or unsubstituted C1 to C20 alkylene group, and R c is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and n is an integer from 1 to 3.

2. The semiconductor photoresist composition according to claim 1, wherein n is an integer of 1 or 2.

3. The semiconductor photoresist composition according to claim 1, wherein R 1 for Substituted or unsubstituted C1 to C10 alkyl, Substituted or unsubstituted C3 to C10 cycloalkyl, Substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, a substituted or unsubstituted C6 to C20 aryl group, or L a -OR a , where L a is a substituted or unsubstituted C1 to C10 alkylene group, and R a is a substituted or unsubstituted C1 to C10 alkyl group.

4. The semiconductor photoresist composition according to claim 3, wherein R 1 is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, or a combination thereof, and R a is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, or a combination thereof.

5. The semiconductor photoresist composition according to claim 1, wherein R 2 for halogen, -OR b , where R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, -O(CO)R 6 , where R 6 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, -NR 7 R 8 , where R 7 and R 8 are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, -NR 9 (COR 10 ), where R 9 and R 10 are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, or -NR 11 C(NR 12 )R 13 , where R 11 , R 12 and R 13 Each is independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

6. The semiconductor photoresist composition according to claim 5, wherein R 2 for halogen, -OR b , where R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, or -O(CO)R 6 , where R 6 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

7. The semiconductor photoresist composition according to claim 5, wherein R 2 -O(CO)R 6 , where R 6 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

8. The semiconductor photoresist composition according to claim 5, wherein R b is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof, and R 6 is hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof.

9. The semiconductor photoresist composition according to claim 1, wherein R 3 to R 5 each is independently hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof.

10. The semiconductor photoresist composition according to claim 1, wherein The organotin compound is represented by any one selected from the compounds listed in Group 1, Group 1 11. The semiconductor photoresist composition according to claim 1, wherein The amount of the organic tin compound is 1 wt % to 30 wt % based on 100 wt % of the semiconductor photoresist composition.

12. The semiconductor photoresist composition according to claim 1, wherein The semiconductor photoresist composition further comprises the following additives: a surfactant, a cross-linking agent, a leveling agent or a combination thereof.

13. A method for forming a pattern, comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition according to any one of claims 1 to 12 on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; as well as The etching target layer is etched using the photoresist pattern as an etching mask.

14. The method of claim 13, wherein the photoresist pattern is formed by applying light having a wavelength of 5 nm to 150 nm.

15. The method according to claim 13, wherein The photoresist pattern has a width of 5 nanometers to 100 nanometers.

Images